New degradable thermosets obtained by cationic copolymerization of DGEBA with an s(γ-butyrolactone)

Diglycidylether of bisphenol A (DGEBA) was cured with different proportions of 1,6-dioxaspiro[4.4]nonane-2,7-dione (s(γ-BL)) with ytterbium triflate as initiator. The curing was studied with differential scanning calorimetry (DSC) and Fourier transform infrared in the attenuated total reflection mode (FTIR/ATR). FTIR/ATR was used to monitor the competitive reactive processes and to quantify the conversion of the epoxide, lactone and intermediate spiroorthoester (SOE) groups. The shrinkage undergone during curing was monitored by means of thermomechanical analysis (TMA). By combining the results obtained by FTIR/ATR and TMA, the processes that were and were not responsible for shrinkage were identified. The thermal and dynamic mechanical properties of the cured materials were determined by DSC and by dynamic mechanical thermal analysis (DMTA), respectively. The kinetic triplet associated with calorimetric curing was determined by means of isoconversional analysis. An increase in the proportion of lactone results in an increased curing rate, a decrease in shrinkage after gelation and a decrease in the glass transition temperature (T_g). Finally, as a preliminary measure, we examined the potential of the systems studied as reworkable materials by means of hydrolytic and thermal degradation. An increase in the ester units in the network results in materials that are less thermally stable and whose controlled degradability is greater.     

Copolymerization of diglycidylether of bisphenol A and bicyclic bis(γ‐lactone)s using rare earth metal triflates as initiators studied with infrared spectroscopy

The thermal cationic curing of mixtures, in various proportions, of diglycidylether of bisphenol A with two substituted condensed bis(γ‐lactone)s initiated using scandium, ytterbium and lanthanum triflates or a conventional boron trifluoride monoethylamine (BF₃·MEA) initiator was investigated. The evolution of the various reactive groups was followed by means of attenuated total reflection Fourier transform infrared spectroscopy. The formation of mono‐spiroorthoesters (monoSOE)s and bis‐spiroorthoesters (bisSOE)s is discussed. The polymerization of bisSOE structures led to the formation of ether–ester–ketone repeat units, which implied the cationic polymerization took place by a tandem reaction. The use of scandium triflate as an initiator led to the highest chemical incorporation of lactone in the network. Moreover, this initiator was the most active, incorporating a higher proportion of lactone in a shorter time. In contrast, the conventional BF₃·MEA initiator incorporated the lowest proportion of bislactone in the cured material. Copyright © 2010 Society of Chemical Industry     

Crosslinking of mixtures of DGEBA with 1,6-dioxaspiro[4,4]nonan-2,7-dione initiated by tertiary amines. Part IV. Effect of hydroxyl groups on initiation and curing kinetics

The anionic homopolymerization of DGEBA epoxy resin and its anionic copolymerization with a bislactone was studied using two alternative tertiary amines, 1-methylimidazole (1MI) and dimethylaminopyridine (DMAP) as initiators. 1MI caused slower cure than DMAP in neat DGEBA and DGEBA-bislactone formulations. Studies of the influence of the hydroxyl concentration in the DGEBA oligomer on its homopolymerization explain descrepancies in the literature regarding the ability of these initiators to produce full cure of the epoxy groups. In contrast, in the copolymerization of DGEBA-bislactone formulations, full cure could be readily achieved with either 1MI or DMAP as initiators, irrespective of the hydroxyl content. FTIR and DSC experiments show that this behaviour is associated with the formation of the carboxylate anion which plays an important part on the curing kinetics and the completion of cure.     

Correlation of fatty acid unsaturation of the major liver mitochondrial phospholipid classes in mammals to their maximum life span potential

Free radical damage is considered a determinant factor in the rate of aging. Unsaturated fatty acids are the tissue macromolecules that are most sensitive to oxidative damage. Therefore, the presence of low proportions of fatty acid unsaturation is expected in the tissues of long-lived animals. Accordingly, the fatty acid compositions of the major liver mitochondrial phospholipid classes from eight mammals, ranging in maximum life span potential (MLSP) from 3.5 to 46 yr, show that the total number of double bonds is inversely correlated with MLSP in both phosphatidylcholine (PtdCho) and phosphatidylethanolamine (PtdEtn) (r = 0.757, P < 0.03, and r = 0.862, P < 0.006, respectively), but not in cardiolipin (P = 0.323). This is due not to a low content of unsaturated fatty acids in long-lived animals, but mainly to a redistribution between kinds of fatty acids on PtdCho and PtdEtn, shifting from arachidonic (r = 0.911, P < 0.002, and r = 0.681, P = 0.05, respectively), docosahexaenoic (r = 0.931 and r = 0.965, P < 0.0001, respectively) and palmitic (r = 0.944 and r = 0.974, P < 0.0001, respectively) acids to linoleic acid (r = 0.942, P < 0.0001, for PtdCho; and r = 0.957, P < 0.0001, for PtdEtn). For cardiolipin, only arachidonic acid showed a significantly inverse correlation with MLSP (r = 0.904, P < 0.002). This pattern strongly suggests the presence of a species-specific desaturation pathway and deacylation-reacylation cycle in determining the mitochondrial membrane composition, maintaining a low degree of fatty acid unsaturation in long-lived animals.     

UV photocatalytic oxidation of paint solvent compounds in air using an annular TiO2‐supported reactor

BACKGROUND: One of the most important industrial sources of volatile organic compounds (VOCs) is related to coating and painting applications. In this sense, photocatalytic oxidation can become an innovative and promising alternative for the remediation of air polluted by VOCs. In this study the UV photodegradation of m‐xylene, toluene and n‐butyl acetate, as representative compounds of paint solvents, was carried out in an annular reactor using a TiO₂–glass wool supported catalyst. RESULTS The removal of each component and their mixture, simulating an industrial emission, was evaluated under different operational conditions. A maximum elimination capacity of 12, 18 and 80 mg C m^?3 s^?1 was reached for m‐xylene, toluene and n‐butyl acetate, respectively. A simple Langmuir–Hinshelwood kinetic model was used to match the experimental data. Photocatalytic oxidation was found to be more effective for all compounds when humidified air was used. CONCLUSIONS: No mass transfer limitation was found under the experimental conditions. n‐butyl acetate was the easiest to degrade and m‐xylene the most recalcitrant. In the abatement of the mixture, competitive adsorption between the pollutants was observed, with the degradation of toluene especially hindered. A nearly linear correlation was found between the UV light intensity and kinetic constants. Copyright © 2010 Society of Chemical Industry     

Additive Role of Immune System Infiltration and Angiogenesis in Uveal Melanoma Progression

Uveal melanoma (UM) is a malignant tumor that arises in the melanocytes of the uveal tract. It is the most frequent eye cancer, and despite new therapeutic approaches, prognosis is still poor, with up to 50% of patients developing metastasis with no efficient treatment options available. In contrast to cutaneous melanoma, UM is considered an “immune-cold” tumor due to the low mutational burden and the unique immunosuppressive microenvironment. To gain insight into the role of the UM microenvironment in regard to prognosis and metastatic progression, we have performed a pool analysis characterizing the UM microenvironment by using a bioinformatic approach. A variety of scores based on gene expression measuring stromal infiltration were calculated and used to assess association with prognosis. As a result, the highest immune and stromal scores were associated with poor prognosis. Specifically, stromal cells (fibroblasts and endothelial cells), T cells CD8+, natural killer (NK) cells, and macrophages M1 and M2 infiltration were associated with poor prognosis. Contrary to other tumors, lymphocytic infiltration is related to poor prognosis. Only B cells were associated with more favorable prognosis. UM samples scoring high in both angiogenesis (Angio) and antigen presentation (AP) pathways showed a poor prognosis suggesting an additive role of both functions. Almost all these tumors exhibited a chromosome 3 monosomy. Finally, an enrichment analysis showed that tumors classified as high Angio-high AP also activated metabolic pathways such as glycolysis or PI3K-AKT-MTOR. In summary, our pool analysis identified a cluster of samples with angiogenic and inflammatory phenotypes exhibiting poor prognosis and metabolic activation. Our analysis showed robust results replicated in a pool analysis merging different datasets from different analytic platforms.     

1-D nanoporous anodic alumina rugate filters by means of small current variations for real-time sensing applications

A rugate filter based on nanoporous anodic alumina was fabricated using an innovative sinusoidal current profile with small current variation. The resulting structure consisted of highly parallel pores with modulations of the pore diameter along the pore axis and with no branching. The effect of the period time and the pore widening post-treatment was studied. From reflectance measurements, it was seen that the position of the reflection band can be tuned by adjusting the period time and the width by pore-widening post-treatments. We tested one of the rugate filters by infiltrating the structure with EtOH and water in order to evaluate its sensing capabilities. This method allows the fabrication of complex in-depth modulated nanoporous anodic alumina structures that open up the possibility of new kinds of alumina-based optical sensing devices.     

Curing and characterization of oxazolidone-isocyanurate-ether networks

Oxazolidone-isocyanurate-ether networks were prepared by copolymerization of mixtures of DGEBA and toluene-2,4-diisocyanate (TDI) in presence of benzyldimethylamine (BDMA) as catalyst. Changes during curing and final properties of the cured materials were investigated by using DSC, FTIR/ATR, TMA, DMTA, TGA, and densitometry. The influence of the molar ratio of isocyanate to epoxide groups on the properties and curing were studied. The kinetics of curing was analyzed by means of an integral isoconversional nonisothermal procedure. The fractions of oxazolidone, isocyanurate, and ether groups present in the final network were evaluated and were found to be dependent on the initial isocyanate/epoxy ratio and curing conditions. By increasing the initial proportion of isocyanate the glass transition temperature, the thermal stability, the shrinkage, and the amount of isocyanurate rings increase, whereas the fraction of ether linkages and oxazolidones decreases. It was observed that the gelation is controlled by the formation of isocyanurate rings at the beginning of the curing. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Procyanidins from pine bark: Relationships between structure,composition and antiradical activity

Barks of Pinus pinaster and Pinus radiata were studied as source of procyanidins; these raw materials, considered a byproduct of forestal industry, were extracted with ethanol. The extract was partially fractionated to obtain an aqueous fraction (FA) containing a great part of the procyanidins from barks and with potential application to both food and medical fields. FAs were rich in polyphenols, 65–87% of which were procyanidins; the mean degree of polymerization (mDP) was 7.9 for radiata (rFA) and 10.6 for pinaster (pFA) varieties.     

An Interplay between Matrix Anisotropy and Actomyosin Contractility Regulates 3D‐Directed Cell Migration

Directed cell migration is essential for many biological processes, such as embryonic development or cancer progression. Cell contractility and adhesion to the extracellular matrix are known to regulate cell locomotion machinery. However, the cross‐talk between extrinsic and intrinsic factors at the molecular level on the biophysical mechanism of three dimensional (3D)‐directed cell migration is still unclear. In this work, a novel physiologically relevant in vitro model of the extracellular microenvironment is used to reveal how the topological anisotropy of the extracellular matrix synergizes with actomyosin contractility to modulate directional cell migration morphodynamics. This study shows that cells seeded on polarized 3D matrices display asymmetric protrusion morphodynamics and in‐vivo‐like phenotypes. It is found that matrix anisotropy significantly enhances cell directionality, but strikingly, not the invasion distance of cells. In Rho‐inhibited cells, matrix anisotropy counteracts the lack of actomyosin‐driven forces to stabilize cell directionality suggesting a myosin‐II‐independent mechanism for cell guidance. Finally, this study shows that on isotropic 3D environments, cell directionality is independent of actomyosin contractility. Altogether, this study provides novel quantitative data on the biomechanical regulation of directional cell motion and shows the important regulatory role of matrix anisotropy and actomyosin forces to guide cell migration in 3D microenvironments.